CN1488784A - Long afterglow luminescent composite fiber and preparation method thereof - Google Patents

Abstract

The invention discloses a long afterglow luminescent composite fiber and a preparation method thereof. The long afterglow luminescent composite fiber of the present invention is prepared in the following way: take luminescent polyamide as the core layer, fiber-forming polymer polyamide, polyester, polyolefin as the skin layer, and carry out composite spinning and make, long afterglow luminescent polyamide The fiber is composed of polyamide and alkaline earth metal aluminate activated by Eu ²⁺ in an effective amount of luminescence. The advantages of the present invention are very significant. The phosphor powder used is the Eu ²⁺ activated alkaline earth metal aluminate series, which is non-toxic , No radioactivity, high luminous brightness, long afterglow time, stable chemical properties. The luminescent polyamide prepared by in-situ polymerization has chemical bonding between the phosphor powder and the polyamide, the phosphor powder is evenly dispersed, not easy to peel off, and has good spinnability. The luminescent fiber prepared by composite spinning has high fiber strength and can be spun Good performance, the fluorescent powder is completely covered in the fiber, the service life is greatly extended, it can be widely used in decoration, clothing, fishery, industry and other fields, and has a good application prospect.

Description

Long afterglow luminescent composite fiber and preparation method thereof

technical field

The invention relates to a luminescent composite fiber, in particular to a long afterglow luminescent composite fiber and a preparation method thereof.

Background technique

Long afterglow luminescent fibers can be used as casual clothing, dresses, warning clothing, decorations, safety signs and so on. The International Maritime Conference has clearly stipulated that on passenger and cargo ships with a capacity of more than 25 people produced after 1998, relevant parts such as passages, fire-fighting equipment and safety and life-saving facilities must be equipped with luminous safety signs to ensure safety. Irradiated luminescent fibers can be used as anti-counterfeiting signs, evening dresses in dance halls, etc.

The development technology of luminescent fibers is closely related to the performance of inorganic luminescent materials. Traditional phosphors are difficult to develop practical luminescent fibers due to their poor stability and radioactivity. Development of Eu ²⁺ activated alkaline earth aluminate phosphors with good chemical stability, non-toxic, non-radioactive, high brightness and long afterglow time, a series of promising luminescent plastics, rubber, coatings, inks, fibers, etc. Successively developed.

Japanese patents JP-A-49-47644, JP-B-3-70020 and JP-A-2-112414 disclose the preparation method of long afterglow luminescent fabrics or fibers. The patent uses traditional phosphor sulfide as the luminescent material, which has poor stability , The fiber luminous brightness is low. The afterglow time is short. If you want to improve the luminous brightness and luminous time of the fiber, you must add certain radioactive elements, which cannot meet the needs of relevant departments.

Compared with other luminescent polymer materials, the preparation technology of luminescent fiber has higher requirements on phosphor powder, so the preparation technology of luminescent fiber is also more difficult. In general, it can be divided into three methods: (1) coating method; (2) blended spinning method; (3) direct spinning method of luminescent polymer.

Patent CN1346857 discloses a luminous coating composition, which is a coating composition composed of adhesive and luminous fibers, and is used for marking objects. The method of coating or printing is relatively simple and can be applied to a variety of fibers and fabrics. The disadvantage is that it is easy to peel off and has a short service life.

The blend spinning method is a more commonly used method for preparing luminescent fibers. Patent CN1081210 discloses a manufacturing method of luminescent fiber at night, which is to add 5-20% luminescent agent to the spinning viscose solution for spinning to prepare luminescent artificial fiber. Patent CN1374415 discloses a manufacturing method of rare earth luminous fiber, which is to add luminous agent and nano additives to the viscous polyester chips to make luminous masterbatch, and then blend and spin with bright polyester chips, but the fiber strength is low . Similarly, patent US6162539 discloses a method for preparing high-brightness fluorescent fibers, which involves blending rare earth phosphors with polyolefin as the core layer, and polyolefin as the skin layer for composite spinning to prepare industrial luminescent polyolefin fibers. Japanese patent JP-A-7-300722 also prepares luminous fibers by composite spinning, and the skin layer is polyester polycaprolactam or polyhexamethylene adipamide, but the added phosphor is susceptible to moisture and affects its luminous brightness.

Contents of the invention

The technical problem to be solved in the present invention is to disclose a long afterglow luminescent composite fiber to overcome the above-mentioned defects in the prior art.

Another technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned long-afterglow luminescent composite fiber, so as to facilitate industrial implementation.

The long afterglow luminescent composite fiber of the present invention is made of luminescent polyamide as the core layer, fiber-forming polymer polyamide, polyester, polyolefin as the skin layer, and composite spinning, and the mass ratio of the core layer to the skin layer is 2 :3～3:1, where:

Said luminescent polyamide is composed of polyamide and Eu ²⁺ activated alkaline earth metal aluminate in an effective amount of luminescence, and the preferred components and weight percentages include: 70% to 98% of polyamide, Eu ²⁺ activated alkaline earth Metal aluminate 2% to 30%.

Said polyamide includes one of polyamide 6, polyamide 66, polyamide 46, polyamide 1010, polyamide 610, polyamide 11, polyamide 12 or polyamide 612;

The alkaline earth metal aluminate activated by Eu ²⁺ is a compound with the general structural formula:

M _X Al _Y O _Z : Eu ²⁺ , N ³⁺

Where: M represents one of Sr, Ca, Mg or Ba;

N represents one of Dy, Nd or Pr;

X=1～4 integer;

Y=2～14 integer;

The integer of Z=4～25;

Preferred Eu ²⁺ activated alkaline earth aluminates include SrAl ₂ O ₄ :Eu ²⁺ , Dy ³⁺ , Sr ₄ Al ₁₄ O ₂₅ :Eu ²⁺ , Dy ³⁺ , CaAl ₂ O ₄ :Eu ²⁺ , One of Nd ³⁺ , BaAl ₂ O ₄ :Eu ²⁺ , Pr ³⁺ , MgAl ₂ O ₄ :Eu ²⁺ , Nd ³⁺ ;

The described Eu2 ⁺ activated alkaline earth aluminates can adopt the methods disclosed in CN1212988 and CN1403533 patents or documents (Chen Zhonglin. Wan Tizhi. Zhang Yuqi. Yan Dezhong, Journal of Illuminating Engineering, 1999, 10 (2), 35) For preparation, commercially available products can also be used, such as YLAG fluorescent powder produced by Shanghai Yuelong New Material Co., Ltd.

Said light-emitting polyamide can preferably be prepared by in-situ polymerization, and its structural features and its preparation method have been described in detail in the inventor's previous Chinese patent, application number 03142085.0, which is briefly described as follows:

Mix the polyamide monomer, additives and water with the above-mentioned fluorescent powder evenly, and react at 200-300°C for 2-8 hours in an inert atmosphere under a pressure of normal pressure to 2.0Mpa, and then continue the reaction under vacuum After 0.2-1 hr, long-lasting luminescent polyamide can be obtained.

Said polyamide monomers include caprolactam, adipic acid, hexamethylenediamine, sebacic acid, decanediamine, butylenediamine, 11-aminoundecanoic acid, lauryl caprolactam, dodecanoic acid. Nylon 66 salt, One or more of nylon 1010 salt or nylon 46 salt;

Said auxiliary agent comprises catalyst or/and stabilizer;

Said catalyst is preferably one of aminocaproic acid or caprolactam;

Said stabilizing agent is preferably a kind of in adipic acid or sebacic acid;

Based on the weight of the polyamide monomer, the catalyst is added in an amount of 1-3%;

The amount of stabilizer added is 0.1-0.6%;

The adding amount of water is 1～35%.

The number-average molecular weight of the light-emitting polyamide is 10,000-15,000.

The preparation method of the long afterglow luminescent composite fiber of the present invention comprises the following steps:

Extract the above-mentioned core component luminescent polyamide in boiling water to remove unreacted monomers and oligomers, and then vacuum dry at 90-100°C for 12-18 hours;

Vacuum-dry the skin layer components mentioned above until the moisture content is less than 50ppm;

Send the dried cortex and core components into a compound spinning machine for melt spinning. The spinning temperature of the core layer is 260-295°C, and the spinning temperature of the cortex is adjusted according to the composition of the cortex, generally 250-290°C. The spinning speed is 1000-3200m/min, and finally stretching or stretching is carried out, and the stretching ratio is 1.6-3.5 times, that is, the long afterglow luminescent composite fiber of the present invention is obtained.

The advantages of the present invention are very remarkable, the phosphor powder used is Eu ²⁺ activated alkaline earth metal aluminate series, non-toxic, non-radioactive, high luminous brightness, long afterglow time and stable chemical properties. Fibers with different light-emitting wavelengths can be developed according to needs; the light-emitting polyamide prepared by in-situ polymerization has chemical bonding between the phosphor and the polyamide, the phosphor is evenly dispersed, not easy to peel off, good spinnability, and in-situ polymerization The molecular weight of the light-emitting polyamide can be adjusted according to the needs, and the light-emitting fibers of different specifications can be spun, and the fiber strength is high; the light-emitting composite fiber of the present invention uses conventional fiber-forming polymers as the skin layer, and has good spinnability. Good stretching or stretching properties, high strength of finished fibers, luminescent composite fibers, with different conventional fiber-forming polymers as the skin, can spin different types of luminescent fibers, and will not affect the process conditions such as fiber dyeing and finishing; Luminescent composite fiber, the fluorescent powder is completely coated inside the fiber, the service life is greatly extended, and it can be widely used in decoration, clothing, fishery, industry and other fields, and has a good application prospect.

Detailed ways

Example 1

Preparation of PA6/PA6 Long Afterglow Luminescent Composite Fiber

Raw materials: Caprolactam 190.4g

    Aminocaproic acid           4.00g

Adipic acid 0.5g

Distilled water 6.00ml

Phosphor powder: CaAl ₂ O ₄ :Eu ²⁺ , Nd ³⁺ 10.36g, average particle size: $\stackrel{\‾}{{\mathrm{D.}}_{50}}=18.0\mathrm{\μm}$

  Polyamide 6 (PA6): 300g, number average molecular weight 11500

Preparation:

(1) Add caprolactam, aminocaproic acid, adipic acid, and distilled water into the reactor according to the above proportions, mix evenly, protect with nitrogen, slowly heat to 140°C, stir, slowly raise the temperature to 250°C, and after constant temperature reaction for 5 hours, pump Vacuum was continued for 0.5 hr to obtain luminescent polyamide 6.

(2) Extract the luminescent polyamide 6 in step (1) in boiling water for 0.5 hr, take it out, dry it in the air, and dry it in a vacuum oven at 95° C. for 18 hr, as the core layer component.

(3) Take 300g of polyamide 6 and dry it in a vacuum oven at 95°C for 18 hours as the skin layer component.

(4) The dried cortex and core components are sent to a composite spinning machine for melt spinning, the core spinning temperature is 280°C, the cortex spinning temperature is 285°C, and the spinning speed is 1000m/min, The elongation ratio is 3.0 times.

Results: The specifications of the luminous composite fiber drawn yarn are 100dtex/20f, the intensity is 3.92cN/dtex, and the luminous wavelength is 420-440nm. After 10 minutes of light, it is placed in a dark place for 2 hours, and the afterglow brightness is 1.15mcd/m ² .

Example 2

Preparation of PA6/PET Long Afterglow Composite Fiber

Raw materials: Caprolactam 190.4g

    Aminocaproic acid           4.00g

Adipic acid 0.5g

Distilled water 6.00ml

Phosphor powder: SrAl ₂ O ₄ :Eu ²⁺ , Dy ³⁺ 31.08g, average particle size: $\stackrel{\‾}{{\mathrm{D.}}_{50}}=2.5\mathrm{\μm}$

  Polyethylene terephthalate (PET): 200g, intrinsic viscosity, 0.67

Preparation:

(1) Add caprolactam, aminocaproic acid, adipic acid, and distilled water into the reactor according to the above ratio, mix evenly, protect with nitrogen, slowly heat to 140°C, stir, slowly heat up to 210°C, react for 1 hour, add fluorescent powder, continue to heat up to 250°C, and after constant temperature reaction for 4.5 hours, continue vacuuming for 0.5 hours to obtain luminescent polyamide 6.

(2) Extract the luminescent polyamide 6 in step (1) in boiling water for 0.5 hr, take it out, dry it in the air, and dry it in a vacuum oven at 95° C. for 18 hr, as the core layer component.

(3) Take 200g of PET and dry it in a vacuum oven at 140°C for 24 hours as the skin layer component.

(4) The dried cortex and core components are sent to a composite spinning machine for melt spinning, the core spinning temperature is 285°C, the cortex spinning temperature is 290°C, and the spinning speed is 2500m/min, The stretch ratio is 2.5 times.

Results: The specifications of the luminous composite fiber drawn yarn are 72dtex/24f, the intensity is 3.82cN/dtex, and the luminous wavelength is 510-525nm. After 10 minutes of light, it is placed in a dark place for 2 hours, and the afterglow brightness is 1.15mcd/m ² .

Example 3

Preparation of PA66/PA66 Long Afterglow Luminescent Composite Fiber

Raw material: PA66 salt 200g

Adipic acid 1.80g

  Caprolactam       4.00g

Distilled water 60g

Phosphor powder: SrAl ₁₄ O ₂₅ :Eu ²⁺ , Dy ³⁺ 20g, average particle size: $\stackrel{\‾}{{\mathrm{D.}}_{50}}=5.8\mathrm{\μm}$

  Polyamide 66 100g, number average molecular weight, 12000

Preparation:

(1) Add PA66 salt, adipic acid, caprolactam, distilled water, and fluorescent powder in the above raw materials into the high-pressure reactor, mix well, pass _N2 to drive off the air, airtight, slowly heat to 210°C, react for 2 hours, stir, and continue to slowly Raise the temperature to 270°C, control the pressure at 1.47-1.96Mpa, continue the reaction for 2 hours, then release to normal pressure, continue the reaction for 3 hours, then vacuumize and continue the reaction for 0.5 hours to obtain polyamide 66.

(2) Extract the luminescent polyamide 66 in the step (2) in boiling water for 15 minutes, take it out, dry it in the air, and dry it in a vacuum oven at 90°C for 16 hours.

(3) Take 100g of polyamide 66 and dry it in a vacuum oven at 90°C for 18 hours as the skin layer component.

(4) The dried cortex and core components are sent to a composite spinning machine for melt spinning, the core spinning temperature is 275°C, the cortex spinning temperature is 285°C, and the spinning speed is 1200m/min, The elongation ratio is 3.5 times.

Results: The specification of luminescent PA66/PA66 composite drawn yarn is 100dtex/20f, the intensity is 4.12cN/dtex, and the luminous wavelength is 485-495nm. After 10 minutes of light, it is placed in a dark place for 2 hours, and the afterglow brightness is 1.52mcd/m ² .

Example 4

Preparation of PA66/PP Long Afterglow Luminescent Composite Fiber

Raw material: PA66 salt 200g

Adipic acid 1.80g

                                                                                                                           

Distilled water 60g

Phosphor powder: SrAl ₁₄ O ₂₅ :Eu ²⁺ , Dy ³⁺ 30g, average particle size: $\stackrel{\‾}{{\mathrm{D.}}_{50}}=8.0\mathrm{\μm}$

  Polypropylene (PP) 70g, melt index 20

Preparation:

(1) Add PA66 salt, adipic acid, caprolactam, distilled water, and fluorescent powder in the above raw materials into the high-pressure reactor, mix well, pass _N2 to drive off the air, airtight, slowly heat to 210°C, react for 2 hours, stir, and continue to slowly Raise the temperature to 270°C, control the pressure at 1.47-1.96Mpa, continue the reaction for 2 hours, then release to normal pressure, continue the reaction for 3 hours, then vacuumize and continue the reaction for 0.5 hours to obtain polyamide 66.

(2) Extract the luminescent polyamide 66 in the step (2) in boiling water for 15 minutes, take it out, dry it in the air, and dry it in a vacuum oven at 90°C for 16 hours.

(3) 70 g of polypropylene was taken, dried in a vacuum oven at 105° C. for 5 hr, and used as the skin layer component.

(4) The dried cortex and core components are sent to a composite spinning machine for melt spinning. The core spinning temperature is 275° C., the cortex spinning temperature is 260° C., and the spinning speed is 1000 m/min. The elongation ratio is 3.5 times.

Results: The specification of luminous PA66/PP composite drawn yarn is 200dtex/20f, the intensity is 3.85cN/dtex, and the luminous wavelength is 485-495nm. After being illuminated for 10 minutes and placed in a dark place for 2 hours, the afterglow brightness is 1.98mcd/m ² .

Example 5

Preparation of PA6/PE Long Afterglow Composite Fiber

Raw materials: Caprolactam 190.4g

    Aminocaproic acid           4.00g

Adipic acid 0.5g

Distilled water 6.00ml

Phosphor powder: SrAl ₂ O ₄ :Eu ²⁺ , Dy ³⁺ 22g, average particle size: $\stackrel{\‾}{{\mathrm{D.}}_{50}}=2.8\mathrm{\μm}$

  Polyethylene (PE): 80g, melt index 26

Preparation:

(1) Add caprolactam, aminocaproic acid, adipic acid, and distilled water into the reactor according to the above ratio, mix evenly, protect with nitrogen, slowly heat to 140°C, stir, slowly heat up to 210°C, react for 1 hour, add fluorescent powder, continue to heat up to 250°C, and after constant temperature reaction for 4.5 hours, continue vacuuming for 0.5 hours to obtain luminescent polyamide 6.

(2) Extract the luminescent polyamide 6 in step (1) in boiling water for 0.5 hr, take it out, dry it in the air, and dry it in a vacuum oven at 95° C. for 18 hr, as the core layer component.

(3) Take 80g of PE and dry it in a vacuum oven at 105°C for 4 hours as the skin layer component.

(4) The dried cortex and core components are sent into a composite spinning machine for melt spinning, the core spinning temperature is 265°C, the cortex spinning temperature is 250°C, and the spinning speed is 1000m/min, The elongation ratio is 3.3 times.

Results: The specifications of the luminescent composite fiber drawn yarn are 72dtex/24f, the intensity is 3.79cN/dtex, and the luminous wavelength is 510-525nm. After being illuminated for 10 minutes and placed in a dark place for 2 hours, the afterglow brightness is 1.24mcd/m ² .

Claims (9)

1. A long afterglow luminescent composite fiber is characterized in that it is made of luminescent polyamide as the core layer, fiber-forming polymer polyamide, polyester, and polyolefin as the cortex, and composite spinning is carried out, and the core layer and the cortex are The mass ratio is 2:3-3:1, wherein: said luminescent polyamide is composed of polyamide and alkaline earth metal aluminate activated by Eu ²⁺ in an effective amount of luminescence. 2. The long-lasting luminescent composite fiber according to claim 1, characterized in that the composition and weight percentage of luminescent polyamide include: 70%-98% of polyamide, Eu ²⁺ activated alkaline earth metal aluminate 2 %~30%. 3. The long afterglow luminescent composite fiber according to claim 1, characterized in that said polyamide includes polyamide 6, polyamide 66, polyamide 46, polyamide 1010, polyamide 610. Polyamide 11. polyamide One of amide 12 or polyamide 612. 4. The long-lasting luminous composite fiber according to claim 1, characterized in that, the alkaline earth aluminate activated by Eu ²⁺ is a compound with the following general structural formula: M _X Al _Y O _Z : Eu ²⁺ , N ³⁺ Where: M represents one of Sr, Ca, Mg or Ba; N represents one of Dy, Nd or Pr; X=1～4 integer; Y=2～14 integer; Integer of Z=4-25. 5. The long-lasting luminescent composite fiber according to any one of claims 1 to 4, characterized in that the Eu ²⁺ activated alkaline earth metal aluminate includes SrAl ₂ O ₄ : Eu ²⁺ , Dy ³⁺ , Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ , Dy ³⁺ , CaAl ₂ O ₄ : Eu ²⁺ , Nd ³⁺ , BaAl ₂ O ₄ : Eu ²⁺ , Pr ³⁺ , MgAl ₂ O ₄ : Eu ²⁺ , Nd ³ One of ⁺ . 6. The method for preparing the long afterglow luminescent composite fiber according to any one of claims 1 to 5, characterized in that it comprises the following steps: Extracting the luminescent polyamide as the core component in boiling water, and then vacuum drying; Carry out vacuum-drying with described cortex component; The dried skin layer and core layer components are sent to a composite spinning machine for melt spinning. 7. The method according to claim 6, characterized in that the skin and core components are vacuum-dried at 90-100° C. for 12-18 hr. 8. The method according to claim 6, characterized in that the skin and core components are vacuum-dried to a moisture content <50 ppm. 9. The method according to claim 6, characterized in that the spinning temperature of the core layer is 260-295° C., the spinning temperature of the cortex is 250-290° C., the spinning speed is 1000-3200 m/min, and finally drawing Stretching or stretching, the stretching ratio is 1.6 to 3.5 times.